Metal ornamentation.



HANNIUA l Parent Fries,

GOODWIN, OF NEWARK, NEW JERSEY.

ME :AL QRNAMENIA l IUN.

SIECIFICATION forming part of Letters Patent No. 670,277, dated March19, 1901. Application filed January 20,1892. Serial No. 418,700. (Nospecimens.)

T0 a l/l whom [(3 may concern:

lie it known that i, HANNIBAL GOODWIN, a citizen of the United States,residing at Newark, in the county of Essex and State of New Jersey, haveinvented certain new and useful Improvements in Methods of PreparingPlates for Decoration or Utility; and I do hereby declare the followingto be a full, clear, and exact description of the invention, such aswill enable others skilled in the art to which it appertains to make anduse the same.

This invention has for its objects, stated generally, the securingupon'metal by chem ical and electrochemical means designs in anothermetal for utility or ornament, in sharper and clearer outline, and infiner definition of detail and with a greater facility and certaintythan have hitherto been obtained.

The invention relates to that class of processes represented by thosedescribed in my prior patents, Nos. 444,951, 459,136, and 459,137.

The invention consists in the improved process of preparing plates fordecoration or utility, all substantially as will be hereinafler setforth, and finally pointed out in the claims.

Among the defects hitherto in the formation of a metallic design in onemetal facing on or upon a bed of another metal by means of stripping allportions of the metal facing except fill those constituting the designone has been the great difficulty of preserving thedesigu from the lossof a certain amount of sharpness, fineness, and definition of detallarising both from the irregular action of the stripping agent and froman inadequate iinene'ss,sharpness, and delicate outline of the resistingdesign-as, for example, in th latter case the resisting designs appliedin viscid organic matter, such as asphaltum, by hand and brush did notand could not possess those qualities/of sharpness and detailcontemplated in this invention. To avoid these defects, I employ on myplate a resistingdesign of such sharpness and perfection of detail ascannot be produced by t e hand and brush, a I employ a chemiml strippingagent wh on entails no raggedness or uneven ness upon the completedmetallic design,

Among the defects hitherto the process of forming upon the bed metal ametallic detendency of the deposited metal topenetrate through theresisting matter designed to exclude the said deposition metal andthenadhere to the bed metal. 'lo avoidthis defect,

sign by electrodeposition one has been the I render the said portions ofthe bed metal non-adherent.

The chief defect hitherto lll engraving tleihnor those port ions of thebed plate not co ered by the design when it is required to enhance theornamental effect or to employ the plate for other utilities has beenthe-injury done to the outline of the remaining design by the mordantemployed for engraving the bed metal. To avoid this defect, I employsuch metals for the design as are not affected by the morda-nt used inthe process of engraving.

In carrying into elfect that part of the invention which relates to theformation of an ornamental or otherwise useful inctallic-de-- sign on abed metal by the stripping otlthe portions of the metal adjacent to thedesign I first proceed by any of the well-known methods to face a plateof metal or an article of metal ware witna facing of silver or gold orplatinum, these metals being the most ornamental and also most resistingto engravingmordauts, both because of the electronegati re relation tothe bed-plate which they ordinarily assume when minersed in etchingagents and because of more or less-inherent iusolubility in most of saidmondants. I next proceed to apply to said facing a resist ing'design inorganic matter, whichl preferably apply by means of some one of the\\'oll-l nown photographic methods, because such a method requires lesslabor and less artistic skill and yet secures the utmost sharp ness ofoutline and delicacy of detail, and this method is industrially useful.matter thus employed may consist of an atten uatcd film of gelatinphotographic-ally impressed directly on this. plate and preferablycovered with a coating of fatty ink and rein forced by someresisting-dust. There are other methods of forming a suitable design inresisting organic matter too well known to require specification. Thedesign having been thus applied, l next proceed to strip away thoseportions of the facing not protected by The organicv loo the design by aprocess which is one of the features of my invention and which just hereI must distinguish from other processes employed'for similar purposes.

Two other processes have hitherto been employed for stripping one metalfrom another, both of which when used. for stripping such metals assilver, adesign in organic matter applied as above doscribedare attendedwith such defects as renderthem for the purposes of the inventionindustrially useless. One of these processes referred to consists insubjecting the metallically-faced plate or were as an anode in'anelectrolyte consisting of cyanid of potassium; but while this process issuccessful in'stripping the metallic facing it is fatal in that it alsostrips away the design in organic matter and then renders liablethe'stripping away of allthe facing. Cyanid as an electrolyte ispowerfully detergent ora destroyer of organic matter. The other and morecommonly em; ployed processofstripping one metal from another is that bystrong acids. There are several serious defects in this acid processwhen applied for the purposes of this invention. Acids appear toproduce, between the bedplate and the facing metal, a galvanic currentwhich seems to render the formation of an electi-onegative .facingdifiicult in most cases and in some cases impossible and all the more soin proportion as the negative metals possess highly electricalconductivity. Either gold or platinum or silver is not only a facileconductor, but when immersed in an acid and in cont-act with most othermetals becomes highly electronegative, and, as is well, known, such ametal standing in such a relation is rendered extremely difficult. todissolve if not quite insoluble, though it would be quite soluble ifunconnected with another metal less negative it were immersed in thesame acid. For example, silver immersed by itself in a moderately-strongsolut ion of acid is readily dissolved, but if connected with a lessnegative metal in the same acid it, under the influence of the voltaiccurrent, becomes quite'insoluble, or silver, if immersed alone in aquaregia, solved, but if connected as above aqua regia is powerless.current between the bed metal and the electronegative facing contributesto another very serious defect in the acid process? of stripping. Theincreased insolubility of the facings thus caused by the cur reutdemands an increased strength of acids to strip them,

and that entails damage uroh the organic matter constituting the do ign. The acids hitherto'employed for the specified metals have been aquaregia a mixt-prc of concentrated nitric and hydrochloric acidsfol-stripping gold and platinum, and a llll Xltl'lb of unicentratedsulfuric and nitric acids for stripping silver. Nitric acid alone hasbeen unavailing for stripping either gold, platinum. or silver, so alsohas hydrochloric, and

gold, and platinum bearing is rapidly dis- 'lhisgeneratiou of a voltaicthis latter acid would dissolve silverdid itnot avail myself of when Icometo etch down a bed metal bearing a design in silver by means ofachlorin-imparting mordant,.such as chlorid ofiron but theforegoiugacidswhich have proved successful in stripping away the facings are nqt lesssuccessful in stripping all such designs in organic matter as can beem-. ployed for the purposes of this in ventiou, and even if such adesign could prove sufiiciently resisting there would in consequence ofthe violent action of the acids be entailed upon the remainingunderlying ornamental metal design a ruggedness unevenness of line asanother defect ins ipping by-the acid. process, and a furtherobjectionnot to be overlooked -to the use of strong acids is the stilling fumesinimicttl to health as well as severely disagreeable.

I now come to my process of strippingas distinguished from thoseheretofore employed. Having, as above described, faced the bed metalwith either silver or gold or platinum and having imposed thereon adesign in resisting matter, I now proceed to strip away those portionsof the facing not covered by the design by subjecting the plate as ananode to an electrolyte containing in solution free iodin and free iodidof potassium, the iodin uniting with the facing to form an iodid or saltof the metal and the iodid of potassium dissolving away the salt as fastas formed. Free bromin may be employed withthe iodin, but its useconfers no advantage over that of iodin alone, and bromid of potassinmmay be employed singly or in combination with theiodid of potassium, butits use confers no advan tageover that of the iodid of potassium singly.Instead of stripping the facing by subjecting it as an anode I maysimply immerse it in the above.specified menstruum; but the electrolytemethod is pret erable because more rapid. Also I may omit from themenstruum free iodin byemployiug the iodid of potassium in concentratedor ap' vproximateIy-concentrated solution, although by this substitutionthe process of stripping is not only slower, but is more expensive. Thisprocess of stripping is distinguished by its results and by its mode ofoperation. It does notgenerate between the bed metal and its tacingavoltaic current. It etfects the st riptoo pingwith facility andcertainty without detaching or injuring the organic matter constitutingthe design. It works with a genllenessthat entails no ruggedness orunevenness upon the remaining ornamental metallic design and it developsno noxious fumes.

Though in the process of dissolving a metal by acids there isformedfirst a chemical compound of the metal which is simultaneously dissolvedby thosm'rounding the solution, and though in this respect my processdoes not differ from the acid process,

acid to complete yet there are additional features and condi tions in mymethod which distinguishes it and by which the beneficial results areobtained. In theformcr process the faced plate to be stripped isimmersedin acid, and acid is a condition for excitation of a galvanic currentbetween the plate and the facing. in my process the plate is immersednot in an acid, but in a neutral liquid. In the acid process thecompound of the metal formed by borrowing an element from the decomposedacid is necessarily as well as sim ultaneonsly dissolved away by theacid to which it owes its existence and by nothing else. in my processthe iodid compound may be formed independently of the specific menstrnumwhich may be chosen to dissolve it away. lhere are many menstruums ofiodin which arenot solvents of iodid compounds. An alcoholic menstruumof iodin will form on the metal facing an iodid of the metal, but itwill not dissolve away that salt to complete the stripping, neither willan ammoniacal menstrnum nor a menstruum thatis chiefly aqueone. A cyanidof potassium menstruuin of iodin will complete the stripping, butunfortunately it also strips the organic matter of the design.Hyposulfite of soda is also a menstruum of iodin capable of completingthe stripping; but in the process it is liable to develop andliberate'an amount of acid adequate to the excitation of a galvaniccurrent. lodid of potassium in solution is the 'menstr-uum of iodincapable of completing the stripping with facility and certainty and inall respects satisfactorily. It is therefore 4 apparent that in thisstripping process the iodin is 'no more important than is the selec tionof the one every way qualified mcnstrnu m of iodin out of the many thatare less ef- Having by this stripping process secured upon a metal plateor metalware a remaining design in silver, gold, or platinum, l haveaccomplished one purpose of the invention. If, however, I desire toenhance the ornamental effect of the design or secure other usefuladvantages, I may next proceed to etch down the portions of ,thebed-plate from which the facing has been removed, and for this purposelomploy a mordant which does not attack the specific metalcox'istitutiug the aforesaid remaining design.

When it is proposed to secure a reversal of above effects prior to thelast stage of engraving, whether by stripping away just that portion ofthe facing lying under the applied design the first and only resultsought for or by proceeding further to deposit in the place of saidlast-stripped portions adifferent metal which in its turn may serve as aresisi or serve for ornamental effect as a second result, I proceed asfollows: I flow t" 'a plate with a solution of matter as lac or oenzoinwhich is not soluble in the solvent of the applied design, and then byWell-known means dissolve out the applied organic design, thus leavingon the adjacent portions the lac as an organic resist and the undermetallic film 0f the design bare. Now this bared metallic filmcorresponding exactly to the organic part of the design removed,'being ametal with which the plate was faced, sustains to its bed-plate theelectrical and other relations before named. It is eitherelect-renegative or by nature insoluble in selected mordants or is bysuch mordants rendered insoluble and is now to be dissolved or strippedaway as the first result proposed, and to effect this i employ thestripping process which i have above described as my invention. If it isproposed to proceed to the second stage of this reversal process anddeposit in place of the duplux design just removed, as last described,another metallic design of different metal, which in its turn may serveeither for ornamental effect or as a resist in securing the purposes ofthis invent-ion, I do before taking the first step in this reversalprocessthat is, before flowing the plate with the lac solution-proceedto render those parts of the plate not occupied by the design incapableof holding adhesively that electrodeposition of metal by which theproposed design is to be effected, and for this reason the depositionmetal will not only go and adhere to the bared parts, but will penetratethrough the lac and to the parts of the plate covered by the lac andadhere there unless those parts are beforehand prepared to resist suchadherence Accordingly befmie flowing with the lac and the removal ofthedesign I either flow over the surface a slight film of greasy or waxymatter dissolved in acetone or alcohol, either singly or combined, or Iiodize those said parts eithcrby fuming with iodin or immersing theplate in a solution of that element, or before flowing the solution oflacl mix with it a sniiiciency of oily or waxy matter; or for thedeposition of an ornamental or usefulmctalli'c design upon the bed-plateI omit facing said bed metal in the first place with an ornan'ental oruseful metal and first apply the d sign in organic matter-directly uponthe bed-plate, and then, by methods described above, render the bareportions of the bed metal incapable ofholdingadhesively anelectrodeposited metal, then flow the solution of lac or benzcin, andthen dissolve out the organic design by means of a solvent which is nota solvent of the lac.

I am aware that in the electrotyping procsee a metallic surface has beenbrushed'with plumbago torender it incapable of holding adherentlythemetal deposited directly on the surface for which it wasintended; but

I amnot aware that ever before a metallicsuch a portion of the its waythrough the overlying organic film, notwithstanding its express purposewas to prevent such a passage. The surfaces desig- 5 nated being thusprepared, the solution of lac flowed and settled, the design dissolvedaway, and the parts of the plate thereby laid bare being properlycleansed. I next suspend'the plate as a cathode in an electrolyticalsolution in order to secure the desired metallic deposit.

Having thus described the invention, what I claim as new is I 1. Theprocess which consists in imposing upon a metallic surface aflesign inorganic matter, then flowing the plate with a greasy or equivalentmatter to prevent on the parts not covered by the design an adhesionthereto of adeposited metal which penetrates through the resinous, gummyor equivalent matter next to be applied to the parts not covered, thenflowing the said resinous solution, then applying a solvent of thedesign and, removing the same together with the overlying,

grease, and then depositing on the bared de- Isjgn a metal forornamentation or utility, the grease on the adjacent portions, servingto c ifine adhesively said deposit to just the parts from which thedesign was removed,

substantially as set forth.

2. The p'rocess which consists in imposing upon a metal bed, a design inorganic matter, the'n flowing the plate with a greasy or equivalentmatter to prevent on the parts not cov- 5 ered by the design an adhesionthereto of a deposited metal which penetrates through the resinous,gummy or equivalent matter next to be applied-to the parts not vcovered,then flowing the said resinous solution, then 0 applying a solvent ofthe design and removing the same together with the overlying grease,then depositing on the bared design a metal capable of being convertedinto an insoluble chlorid of the metal, the grease on 5 the adjacentportions serving to confine adherently saiddpposit to just the partsfrom W removed and then applying a chlorin-evolving solution or sulfurelement to render-insoluble the deposited metal by converting into acompound of the electrodeposit as forces as set forth.

3. The process which consists in imposing 1 upon a metal bed a designinorganic matter, then flowing the plate with a greasy or equiv: alentmatter to prevent on the parts not covered by the design an adhesionthereto of a deposited metal which penetrates through the resinous orgummy matter next to be applied to the parts not covered, then flowingthe said resinous or gummy solution, then applying a solvent of thedesign and removing the same together with theoverlying grease, thendepositing on the bared design a layer of silver and then with chloridof iron or equivalent chlorinating-agent, etching down the bed metal,and converting the exposed portions of the deposited silver design intoan insoluble chlorid of silver tlie said insoluble chlorid serving as aresist to the bed-etching fluid, substantially as set forth.

4. The process which consists in imposing upon a metal bed a design inorganic matter, then flowing the plate with a greasy or Edit?-alentmatter to prevent on the pa'tts no covl ered by the design anadhesion thereto 0! deposited metal which penetrates through the.

resinous or gummymatter next to be applied to the parts not covered,then flowing the said resinous orgummy solution, then ap lyings solventof the design and removing t same together with the overlyinggrease.then (10- has been removed an electrodeposition of ametal.electronegativetothat ofthehed-plate, the grease on the adjacentporvtionrs sen'ing I positing on the parts. from which the'design toconfine adhesively said depoplt .tojnstthe.

leaving the bed-plate to be etched downythm electronegatite depositedmetal serving as a" resist against the bed-etching agent, mum tially asset forth.

In testimony have hereunto December, 1891.

HANNIBAL feoon wit;

Witnesses:

CHARLES H. PnLL, OSCAR A. Miormn.

that I claim the*foregoingl l parts from whieh the design was removed,'set my hand this Nthday of i

